US10577436B2 - Polymerization system using double click michael addition and photopolymerization - Google Patents

Polymerization system using double click michael addition and photopolymerization Download PDF

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US10577436B2
US10577436B2 US15/743,637 US201615743637A US10577436B2 US 10577436 B2 US10577436 B2 US 10577436B2 US 201615743637 A US201615743637 A US 201615743637A US 10577436 B2 US10577436 B2 US 10577436B2
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alkyl
aryl
derivatives
acrylate
monomer
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US20180319936A1 (en
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Matthieu RETAILLEAU
Ahmad IBRAHIM
Xavier Allonas
Céline CROUTXÉ-BARGHORN
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Universite de Haute Alsace
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/60—Polymerisation by the diene synthesis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/024—Polyamines containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2280/00—Compositions for creating shape memory

Definitions

  • Some embodiments relate to a dual cure polymerization system combining aza-Michael addition polymerization and photopolymerization.
  • Some embodiments also relate to a dual cure polymerization system for preparing interpenetrating polymer networks.
  • Some embodiments also relate to compositions and articles obtainable by a process of the invention and uses thereof.
  • FIG. 1 is a schematic representation of the aza-Michael addition reaction.
  • FIG. 2 represents chemical structures of the starting materials used in the Examples.
  • FIG. 3 represents in-situ monitoring of reaction progress based on NMR calculated % transformation of the different species consumed or generated at different polymerization stage (reactants and products of Example 1).
  • FIG. 4 represents EBAD conversion kinetics of the three stage process of Example 1.
  • FIG. 5 represents the evolution of thermomechanical properties of the film obtained after Stage 2 and at different polymerization time of stage 3 (Example 1).
  • FIG. 6 represents in-situ monitoring of reaction progress based on NMR calculated % transformation of the different species consumed or generated (SR833s, DP-SR833s and SR833s-DP-SR833s) at different polymerization stage (Example 2). Ratio cadaverine/SR833S 1:4.
  • FIG. 7 represents comparative DSC monitoring of Tg's at different polymerization stage for the AZ1+AZ2 polymerization systems of comparative Example 4.
  • FIG. 8 depicts the results of the pliability tests of Example 6.
  • FIG. 9 illustrates the memory-shape properties of the polymer film of Example 6 according to the invention.
  • Table 1 summarizes in-situ monitoring of reaction progress based on NMR calculated % transformation of the different species consumed or generated).
  • EBAD, DP-EBAD and EBAD-DP-EBAD at different polymerization stage (reactants and products of Example 1 at different polymerization stages of the thermal aza-acrylate Michael addition with feed molar ratio 1:4.2 (Ratio cadaverine/SR349)
  • Table 2 summarizes EBAD conversion and Tg obtained after each of the three stage in Example 1.
  • Table 3 summarizes comparative acrylate conversion and Tg obtained when changing the order of the photopolymerization step.
  • Table 4 summarizes Tg obtained as a function of time with the polymerization system of Example 2.
  • Table 5 summarizes the results of the Persoz tests of Example 6.
  • Table 6 provides the comparative mechanical properties between the composites of Example 7 made according to the invention and purely acrylate polymers.
  • the terms “a,” “an,” “the,” and/or “said” means one or more.
  • the words “a,” “an,” “the,” and/or “said” may mean one or more than one.
  • the terms “having,” “has,” “is,” “have,” “including,” “includes,” and/or “include” has the same meaning as “comprising,” “comprises,” and “comprise.”
  • “another” may mean at least a second or more.
  • substituted refers to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent.
  • substituents contained in formulae of this invention refer to the replacement of hydrogen radicals in a given structure with the radical of a specified substituent.
  • the substituent may be either the same or different at every position.
  • substituted is contemplated to include all permissible substituents of organic compounds.
  • aliphatic includes both saturated and unsaturated, straight chain (i.e., unbranched) or branched aliphatic hydrocarbons, which are optionally substituted with one or more functional groups.
  • aliphatic is intended herein to include, but is not limited to, alkyl, alkenyl, alkynyl moieties.
  • alkyl refers to straight and branched alkyl groups. An analogous convention applies to other generic terms such as “alkenyl”, “alkynyl” and the like.
  • lower alkyl is used to indicate those alkyl groups (substituted, unsubstituted, branched or unbranched) having about 1-6 carbon atoms.
  • Illustrative alkyl groups include, but are not limited to, for example, methyl, ethyl, n-propyl, isopropyl, allyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, sec-pentyl, isopentyl, tert-pentyl, n-hexyl, sec-hexyl, moieties and the like, which again, may bear one or more substituents.
  • Alkenyl groups include, but are not limited to, for example, ethenyl, propenyl, butenyl, 1-methyl-2-buten-1-yl, and the like.
  • Representative alkynyl groups include, but are not limited to, ethynyl, 2-propynyl (propargyl), 1-propynyl and the like.
  • alicyclic refers to compounds which combine the properties of aliphatic and cyclic compounds and include but are not limited to cyclic, or polycyclic aliphatic hydrocarbons and bridged cycloalkyl compounds, which are optionally substituted with one or more functional groups.
  • alicyclic is intended herein to include, but is not limited to, cycloalkyl, cycloalkenyl, and cycloalkynyl moieties, which are optionally substituted with one or more functional groups.
  • Illustrative alicyclic groups thus include, but are not limited to, for example, cyclopropyl, —CH 2 -cyclopropyl, cyclobutyl, —CH 2 -cyclobutyl, cyclopentyl, —CH 2 -cyclopentyl-n, cyclohexyl, —CH 2 -cyclohexyl, cyclohexenylethyl, cyclohexanylethyl, norbornyl moieties and the like, which again, may bear one or more substituents.
  • cycloalkyl refers specifically to cyclic alkyl groups having three to seven, preferably three to ten carbon atoms. Suitable cycloalkyls include, but are not limited to cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and the like, which, as in the case of aliphatic, heteroaliphatic or heterocyclic moieties, may optionally be substituted.
  • An analogous convention applies to other generic terms such as “cycloalkenyl”, “cycloalkynyl” and the like.
  • heteroalkyl refers to aliphatic or alkyl moieties in which one or more carbon atoms in the main chain have been substituted with a heteroatom.
  • An analogous convention applies to other generic terms such as “heteroalkenyl”, “heteroalkynyl” and the like.
  • a heteroalkyl group refers to an alkyl chain which contains one or more oxygen, sulfur, nitrogen, phosphorus or silicon atoms, i.e., in place of carbon atoms.
  • Heteroalkyl moieties may be branched or linear unbranched.
  • heterocyclic refers to compounds which combine the properties of heteroaliphatic and cyclic compounds and include but are not limited to saturated and unsaturated mono- or polycyclic heterocycles such as morpholino, pyrrolidinyl, furanyl, thiofuranyl, pyrrolyl etc., which are optionally substituted with one or more functional groups, as defined herein.
  • heterocyclic refers to a non-aromatic 5-, 6- or 7-membered ring or a polycyclic group, including, but not limited to a bi- or tri-cyclic group including fused six-membered rings having between one and three heteroatoms independently selected from oxygen, sulfur and nitrogen, wherein (i) each 5-membered ring has 0 to 2 double bonds and each 6-membered ring has 0 to 2 double bonds, (ii) the nitrogen and sulfur heteroatoms may optionally be oxidized, (iii) the nitrogen heteroatom may optionally be quaternized, and (iv) any of the above heterocyclic rings may be fused to an aryl or heteroaryl ring.
  • heterocycles include, but are not limited to, pyrrolidinyl, pyrazolinyl, pyrazolidinyl, imidazolinyl, imidazolidinyl, piperidinyl, piperazinyl, oxazolidinyl, isoxazolidinyl, morpholinyl, thiazolidinyl, isothiazolidinyl, and tetrahydrofuryl.
  • aromatic moiety refers to stable substituted or unsubstituted unsaturated mono- or polycyclic hydrocarbon moieties having preferably 3-14carbon atoms, including at least one ring satisfying the Hückel rule for aromaticity.
  • aromatic moieties include, but are not limited to, phenyl, indanyl, indenyl, naphthyl, phenanthryl and anthracyl.
  • heteroaryl moiety refers to unsaturated mono-heterocyclic or polyheterocyclic moieties having preferably 3-14 carbon atoms and at least one ring atom selected from S, O and N, including at least one ring satisfying the Hückel rule for aromaticity.
  • heteroaryl refers to a cyclic unsaturated radical having from about five to about ten ring atoms of which one ring atom is selected from S, O and N; zero, one or two ring atoms are additional heteroatoms independently selected from S, O and N; and the remaining ring atoms are carbon, the radical being joined to the rest of the molecule via any of the ring atoms, such as, for example, pyridyl, pyrazinyl, pyrimidinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, oxazolyl, isooxazolyl, thiadiazolyl, oxadiazolyl, thiophenyl, furanyl, quinolinyl, isoquinolinyl, and the like.
  • heteroaryl moieties include, but are not limited to, pyridyl, quinolinyl, dihydroquinolinyl, isoquinolinyl, quinazolinyl, dihydroquinazolyl, and tetrahydroquinazolyl.
  • amine refers to a group having the structure —N(R) 2 wherein each occurrence of R is independently hydrogen, or an aliphatic, heteroaliphatic, aryl or heteroaryl moiety, or the R groups, taken together, may form a heterocyclic moiety.
  • halogen refers to an atom selected from fluorine, chlorine, bromine and iodine.
  • the term “independently” refers to the fact that the substituents, atoms or moieties to which these terms refer, are selected from the list of variables independently from each other (i.e., they may be identical or the same).
  • the term “about” can refer to a variation of ⁇ 5%, ⁇ 10%, ⁇ 20%, or ⁇ 25%, of the value specified. For example, “about 50” percent can in some embodiments carry a variation from 45 to 55 percent.
  • the term “about” can include one or two integers greater than and/or less than a recited integer. Unless indicated otherwise herein, the term “about” is intended to include values, e.g., weight percents, proximate to the recited range that are equivalent in terms of the functionality of the individual ingredient, the composition, or the embodiment.
  • the term “and/or” means any one of the items, any combination of the items, or all of the items with which this term is associated.
  • a recited range includes each specific value, integer, decimal, or identity within the range. Any listed range can be easily recognized as sufficiently describing and enabling the same range being broken down into at least equal halves, thirds, quarters, fifths, or tenths. As a non-limiting example, each range discussed herein can be readily broken down into a lower third, middle third and upper third, etc.
  • a dual cure polymerization process including:
  • Steps i) through iii) are carried out in sequential order i) ⁇ ii) ⁇ iii).
  • irradiation step ii) is carried out when step i) is substantially complete.
  • complete means that the aza Michael reaction of step i) has reached a steady state whereby the conversion rate (I) ⁇ (I A ) or (II) ⁇ (II A ) is about zero.
  • the conversion rate may be determined by conventional methods, such as following the reaction by NMR.
  • the reactivity of amines in the case of the Michael addition is as follows: secondary amine (original)>primary amine>2° amine (formed).
  • the polymerization process may be considered as a multi-step method.
  • a photochemical step (ii) may be inserted between the two aza-Michael steps to reinforce the mechanical properties ( FIG. 1 ).
  • the difference in reactivity between AZ1 and AZ2 allows to use photochemistry in a controllable and reproducible way to fine-tune the properties of the end-product.
  • the electrophile monomer if of formula (I) above, wherein R 1 represents H or methyl.
  • a catalyst may be used in the reaction mixture to allow the Michael addition in steps (i) and (iii) to proceed. Accordingly, when R 1 is methyl, steps (i) and (iii) may be carried out in the presence of a suitable catalyst. Any catalyst conventionally used in Michael addition chemistry may be used. Exemplary catalysts include:
  • R 1 is H.
  • the double bond of monomer (I) is reactive to the Michael addition without the need of a catalyst.
  • amines act as Michael addition catalysts.
  • the nucleophile monomer R 3 —NH 2 act as an in situ catalyst.
  • the electrophile monomer (I) represents an acrylate ester monomer, an acrylonitrile monomer, an acrylamide monomer, a maleimide monomer, a cyanoacrylate monomer, a vinylsulfone monomer, an ⁇ , ⁇ -unsaturated ketone monomer, an ⁇ , ⁇ -unsaturated aldehyde monomer, a nitro ethylene monomer, a vinylphosphonate monomer, a vinylpyridine monomer, a ⁇ -keto acetylene monomer, or an acetylene ester monomer.
  • Any acrylate ester, acrylonitrile, acrylamide, maleimide, cyanoacrylate, vinylsulfone, ⁇ , ⁇ -unsaturated ketone, ⁇ , ⁇ -unsaturated aldehyde, nitro ethylene, vinylphosphonate, vinylpyridine, ⁇ -keto acetylene, acetylene ester monomer suitable for Michael addition may be used in the context of the present invention.
  • the electrophile monomer (I) may represent an acrylate ester monomer wherein R 1 and R 2 are each H and EWG 1 represents
  • R B represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR B1 where R B1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R B may represent C 1-20 alkyl, C 1-20 heteroalkyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, or —OR B1 where R B1 represents C 1-6 alkyl; and each of the alkyl moieties may be linear, branched or cyclic.
  • R B represents a linear, branched or cyclic C 1-6 alkyl moiety or a C 6-10 aryl moiety.
  • the electrophile monomer (I) may represent an acrylonitrile monomer wherein R 1 and R 2 are each H and EWG 1 represents
  • the electrophile monomer (I) may represent an acrylamide monomer wherein R 1 and R 2 are each H and EWG 1 represents
  • R C represents H, C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR C1 where R C1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R C represents a linear, branched or cyclic C 1-6 alkyl moiety or a C 6-10 aryl moiety.
  • the electrophile monomer (I) may represent a maleimide monomer having the structure
  • the electrophile monomer (I) may represent a cyanoacrylate monomer wherein R 1 is —CN, R 2 is H, and EWG 1 represents
  • R B represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR B1 where R B1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R B may represent C 1-20 alkyl, C 1-20 heteroalkyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, or —OR B1 where R B1 represents C 1-6 alkyl; and each of the alkyl moieties may be linear, branched or cyclic.
  • R B represents a linear, branched or cyclic C 1-6 alkyl moiety or a C 6-10 aryl moiety.
  • the electrophile monomer (I) may represent a vinylsulfone monomer wherein R 1 and R 2 are each H and EWG 1 represents
  • R D represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR D1 where R D1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R D may represent C 1-20 alkyl, C 2-20 alkenyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, or C 6-10 aryl; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, or —OR D1 where R D1 represents C 1-6 alkyl; and each of the alkyl and alkenyl moieties may be linear, branched or cyclic.
  • R D represents a linear, branched or cyclic C 1-6 alkyl moiety, a C 6-10 aryl moiety or a vinyl moiety.
  • the electrophile monomer (I) may represent an ⁇ , ⁇ -unsaturated ketone monomer wherein R 1 and R 2 are each H and EWG 1 represents
  • R E represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR E1 where R E1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R E may represent C 1-20 alkyl, C 2-20 alkenyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 7-20 aralkyl, C 6-10 aryl, or 5 or 6-membered heteroaryl; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, or —OR E1 where R E1 represents C 1-6 alkyl; and each of the alkyl and alkenyl moieties may be linear, branched or cyclic.
  • R E represents a linear, branched or cyclic C 1-6 alkyl moiety or a C 6-10 aryl moiety.
  • the electrophile monomer (I) may represent an ⁇ , ⁇ -unsaturated aldehyde monomer wherein R 1 and R 2 are each H and EWG 1 represents
  • the electrophile monomer (I) may represent a nitro ethylene monomer wherein R 1 and R 2 are each H and EWG 1 represents —NO 2 .
  • the electrophile monomer (I) may represent a vinylphosphonate monomer wherein R 1 and R 2 are each H and EWG 1 represents
  • R F1 and R F2 independently represent C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 7-20 aralkyl, or C 6-10 aryl; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR FF1 where R FF1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R F1 and R F2 may independently represent C 1-20 alkyl or C 6-10 aryl; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, or —OR FF1 where R FF1 represents C 1-6 alkyl; and each of the alkyl moieties may be linear, branched or cyclic.
  • R F1 and R F2 independently represent C 1-6 alkyl.
  • the electrophile monomer (I) may represent a vinylpyridine monomer having the structure
  • the electrophile monomer (I) may represent a ⁇ -keto acetylene monomer wherein EWG 2 represents
  • R E represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR E1 where R E1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R E may represent C 1-20 alkyl, C 2-20 alkenyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 7-20 aralkyl, C 6-10 aryl, or 5 or 6-membered heteroaryl; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, or —OR E1 where R E1 represents C 1-6 alkyl; and each of the alkyl and alkenyl moieties may be linear, branched or cyclic.
  • R E represents a linear, branched or cyclic C 1-6 alkyl moiety or a C 6-10 aryl moiety.
  • the electrophile monomer (I) may represent an acetylene ester monomer wherein EWG 2 represents
  • R B represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR B1 where R B1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R B may represent C 1-20 alkyl, C 1-20 heteroalkyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, or —OR B1 where R B1 represents C 1-6 alkyl; and each of the alkyl moieties may be linear, branched or cyclic.
  • R B represents a linear, branched or cyclic C 1-6 alkyl moiety or a C 6-10 aryl moiety.
  • each of the foregoing R B , R C , R D , R E , R F1 and R F2 substituents may further bear one or more additional Michael acceptor double-bonds and/or radically polymerizable double bonds.
  • each of the foregoing R B , R C , R D , R E , R F1 and R F2 substituents may further bear one or more acryl or methacryl groups:
  • R′1 represents H or methyl, preferably H. More preferably, each of the R B , R C , R D , R E , R F1 and R F2 substituents may further bear one or more acrylate or methacrylate groups, most preferably acrylate groups.
  • the electrophile monomer (I) may be an acrylate ester, acrylonitrile, acrylamide, maleimide, cyanoacrylate, vinylsulfone, or ⁇ , ⁇ -unsaturated ketone monomer, as further defined above.
  • the electrophile monomer (I) may be an acrylate ester, as further defined above. More advantageously, the electrophile monomer (I) may be an acrylate ester having the structure:
  • R B is as defined above.
  • a dual cure polymerization process including:
  • R B represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR B1 where R B1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic; and wherein R B contains one or more additional Michael acceptor double-bonds and/or radically polymerizable double bonds, for example one or more acryl or methacryl groups:
  • R′1 represents H or methyl, preferably H; more preferably, R B optionally bears one or more acrylate or methacrylate groups, most preferably acrylate groups;
  • R 3 a nucleophile monomer, R 3 —NH 2 , bearing a primary amine functional group wherein R 3 represents the nucleophile monomer radical;
  • R B may represent C 1-20 alkyl, C 1-20 heteroalkyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, or —OR B1 where R B1 represents C 1-6 alkyl; and each of the alkyl moieties may be linear, branched or cyclic.
  • R B represents a linear, branched or cyclic C 1-6 alkyl moiety or a C 6-10 aryl moiety.
  • the acrylate monomer may be any acrylate resin known in the art.
  • the electrophile monomer may be an acrylate, a polyester acrylate, a urethane acrylate, an epoxy acrylate, or a silicone acrylate monomer.
  • Such acrylate resins are commercially available, for example from Sartomer, or Allnex.
  • polyester acrylate monomers we may mention: monofunctional polyester acrylate monomers, bifunctional polyester acrylate monomers (such as, CN2036®, CN2203®, CN2267®, CN2505®, CN2609®, CN2610®), trifunctional polyester acrylate monomers such as CN2634®, tetrafunctional polyester acrylate monomers such as CN203®, CN2555®, CN2560®, CN2295®, CN2303®, CN2305®, CN2562®, CN291®, CN293®.
  • monofunctional polyester acrylate monomers such as, CN2036®, CN2203®, CN2267®, CN2505®, CN2609®, CN2610®
  • trifunctional polyester acrylate monomers such as CN2634®
  • tetrafunctional polyester acrylate monomers such as CN203®, CN2555®, CN2560®, CN2295®, CN
  • urethane acrylate monomers we may mention: monofunctional urethane acrylate monomers; bifunctional urethane acrylate monomers such as CN9001®, CN9002®, CN910A70®, CN9167®, CN9170A86®, CN9200®, CN963B80®, CN964A85®, CN965®, CN966H90®, CN9761®, CN9761A75®, CN981®, CN991®, CN996®; trifunctional urethane acrylate monomers such as CN9245S®, CN9250A75®, CN9260D75®, CN970A60®, CN998B80®; tetrafunctional urethane acrylate monomers such as CN9165A®, CN925®, CN9276®; higher urethane acrylate monomers (functionality >4) such as CN9210®, CN92
  • epoxy acrylate monomers we may mention: monofunctional epoxy acrylate monomers such as CN131B®, CN152®; bifunctional epoxy acrylate monomers such as CN UVE150/80®, CN UVE151M®, CN104®, CN104A60®, CN104A80®, CN104B80®, CN104D80®, CN109®, CN110®, CN116®, CN132®, CN164®, CN186®, CN2003EU®; trifunctional epoxy acrylate monomers such as CN112C60®, CN113D70®, CN122A80®, CN127®; tetrafunctional epoxy acrylate monomers; higher epoxy acrylate monomers (functionality >4) such as CN111®.
  • monofunctional epoxy acrylate monomers such as CN131B®, CN152®
  • bifunctional epoxy acrylate monomers such as CN UVE150/80®, CN UVE151M®, CN104®, CN104
  • silicone acrylate monomers we may mention bifunctional silicone acrylate monomers such as CN9800®.
  • the electrophile monomer may be Tertiobutyl cyclohexanol acrylate (TBCHA), 2-(2-ethoxyethoxy) ethyl acrylate (EOEOEA), C16/C18 alkyl acrylate, Tetrahydrofurfuryl acrylate (THFA), C12 alkyl acrylate (Lauryl acrylate), C12/C14 acrylate, 2-phenoxyethyl acrylate (2-PEA), Isodecyl acrylate (IDA), Ethoxylated 4 phenyl acrylate (P4EOA), 3,3,5-trimethyl cyclohexanol acrylate (TMCHA), Iso octyl acrylate (IOA), Octyl decyl acrylate (ODA), Tridecyl acrylate (TDA), Polycaprolactone acrylate (CAPA), Ethoxylated 4 nonyl phenol acrylate (NP4EOA), Isoborn
  • the electrophile monomer contains one Michael acceptor double-bond, and the nucleophile monomer contains one primary amine functional group.
  • the electrophile monomer contains two Michael acceptor double-bonds, and the nucleophile monomer contains two primary amine functional groups.
  • the electrophile monomer may have the structure:
  • R represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, —OR A where R A represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R may represent C 1-20 alkyl, C 1-20 heteroalkyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl or C 6-10 aryl; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, —OR A where R A represents C 1-6 alkyl; and each of the alkyl moieties may be linear, branched or cyclic.
  • this electrophile monomer may be reacted by a diamine in step (i) of the method of the invention.
  • the nucleophilic monomer R 3 —NH 2 may be any compound bearing a primary amine functional group.
  • the nucleophilic monomer may not contain functional groups that may be more reactive towards the Michael acceptor double-bonds present on the electrophile monomer than primary amines, so as not to compete with the Aza-Michael reaction.
  • the nucleophilic monomer may contain —OH or —SH functional groups which are less reactive than primary amine functional groups towards Michael addition.
  • R 3 represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 6-10 aryl, 5 or 6-membered heteroaryl, or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with —NH 2 , halogen, —CN, C 1-6 alkyl, —C( ⁇ O)OR 3A where R 3A represents C 1-6 alkyl or C 6-10 aryl, or —OR 3B where R 3B represents H, C 1-6 alkyl or C 6-10 aryl optionally further substituted with —NH 2 ; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R 3 may represent C 1-20 alkyl, C 1-20 heteroalkyl, C 7-20 aralkyl or C 6-10 aryl; wherein each of the foregoing groups may be optionally substituted with —NH 2 , C 1-6 alkyl, —C( ⁇ O)OR 3A where R 3A represents C 1-6 alkyl or C 6-10 aryl, or —OR 3B where R 3B represents H, C 1-6 alkyl or C 6-10 aryl optionally further substituted with —NH 2 ; and each of the alkyl moieties may be linear, branched or cyclic.
  • the nucleophilic monomer R 3 —NH 2 may be an aliphatic or cyclo-aliphatic primary amine, such as:
  • the nucleophilic monomer R 3 —NH 2 may be an aromatic primary amine, such as: Ar—CH2-NH2, NH2-Ar—NH2, NH2-CH2-Ar—CH2-NH2, —NH2-Ar—CH2-NH2, Ar—CH2-NH—(CH2)2-NH2, NH2-Ar—Ar—NH2 or NH2-Ar—O—Ar—NH2, wherein Ar represents an optionally substituted phenyl moiety.
  • the nucleophilic monomer R 3 —NH 2 may be an aromatic primary amine, such as:
  • the nucleophilic monomer R 3 —NH 2 may also be an amino ether compound, such as: 4,9-Dioxadodecane-1,12-diamine, 4,7,10-Trioxatridecane-1,13-diamine, 2,2′-(Ethylenedioxy)bis(ethylamine), Poly(ethylene glycol) bis(amine), Polyetheramine D 230, Polyetheramine D 400, Polyetheramine D 2000 or Polyetheramine T 403, all commercially available from BASF.
  • an amino ether compound such as: 4,9-Dioxadodecane-1,12-diamine, 4,7,10-Trioxatridecane-1,13-diamine, 2,2′-(Ethylenedioxy)bis(ethylamine), Poly(ethylene glycol) bis(amine), Polyetheramine D 230, Polyetheramine D 400, Polyetheramine D 2000 or Polyetheramine T 403, all commercially available from BASF.
  • the nucleophilic monomer R 3 —NH 2 may also be an aminoacid, an aminoalcohol (e.g., ethanolamine) or an aminophosphate.
  • the nucleophilic monomer may be 1-hexylamine or 1,5-diaminopentane, preferably 1,5-diaminopentane.
  • the electrophile monomer contains two Michael acceptor double-bonds, and the nucleophile monomer contains two primary amine functional groups, wherein the electrophile monomer may have the structure:
  • R represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, —OR A where R A represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic;
  • the nucleophile monomer has the structure NH 2 R′NH 2 , wherein R′ represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 6-10 aryl, or 5 or 6-membered heteroaryl; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, —OR′ A where R′ A represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic.
  • R may represent C 1-20 alkyl, C 1-20 heteroalkyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl or C 6-10 aryl; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, C 6-10 aryl, —OR A where R A represents C 1-6 alkyl; and each of the alkyl moieties may be linear, branched or cyclic;
  • R′ may represent C 1-20 alkyl, C 1-20 heteroalkyl, C 7-20 aralkyl or C 6-10 aryl; wherein each of the foregoing groups may be optionally substituted with C 1-6 alkyl, —OR′ A where R′ A represents C 1-6 alkyl; and each of the alkyl moieties may be linear, branched or cyclic.
  • the ratio (Michael acceptor double-bonds of the electrophile monomer)/(primary amine functional groups of the nucleophile monomer) may range from 1.1/1 to 100/1, more preferably the ratio may be 1.5/1 to 20/1; most preferably the ratio may be 2/1 to 10/1.
  • the light source used in step ii) may be a UV or visible light source, such as LED, arc lamp, incandescence lamp or natural light.
  • irradiation step ii) is carried out when step i) is substantially complete.
  • step ii) is carried out in the presence of a photoinitiator.
  • Any photoinitiator conventionally used in the art may be used.
  • the photoinitiator may be selected from:
  • the method according to this first aspect of the invention may carried out in the absence of a catalyst and the electrophile monomer has the structure:
  • R B represents C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, or —OR B1 where R B1 represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic; preferably, R B may represent C 1-20 alkyl, C 1-20 heteroalkyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl
  • R B may further bear one or more acryl or methacryl groups:
  • R′1 represents H or methyl, preferably H; more preferably R B may further bear one or more acrylate or methacrylate groups, most preferably acrylate groups.
  • the electrophile and nucleophile monomers are liquid at room temperature, so that the process is carried out at room temperature in the absence of solvent.
  • This solvent-free variant is particularly advantageous as it responds to ever-increasing demands for environmentally-friendly and cost efficient processes.
  • a solvent may be used throughout the process. Any solvent conventionally used in polymer chemistry may be used. Typical solvents for the Aza-Michael reaction include methanol, ethanol, cresol, m-cresol, diethyl ether, tetrahydrofuran, benzene, xylene, toluene, dioxane, water, trifluoroethanol (TFE), hexafluoroisopropyl alcohol (HFIP), acetonitrile, 1,2-Dichloroethane, dichloromethane, poly(ethylene glycol), Dimethylformamide, 1-Butyl-3-methylimidazolium hexafluorophosphate, 1-Butyl-3-methylimidazolium tetrafluoroborate, 2-propanol (iPrOH) ⁇ 2H 2 O, Tetra-n-butylammonium bromide, dimethylsulfoxide
  • step iii) is carried out without additional energy or processing step other than letting the secondary aza-Michael addition reaction proceed at room temperature, thereby allowing the polymer product to spontaneously consolidate.
  • IPN interpenetrating polymer networks
  • EWG 1 and EWG 2 independently may represent:
  • R B , R C , R D , R E , R F1 and R F2 are as defined in claim 2 ;
  • R B , R C , R D , R E , R F1 and R F2 substituents may further bear one or more acryl or methacryl groups:
  • R′1 represents H or methyl, preferably H; more preferably each of the R B , R C , R D , R E , R F1 and R F2 substituents may further bear one or more acrylate or methacrylate groups, most preferably acrylate groups.
  • the electrophile monomer (I) may be an acrylate monomer having the structure:
  • electrophile monomer (II) is a methacrylate monomer having the structure:
  • R EWG1 and R EWG2 independently represent C 1-20 alkyl, C 2-20 alkenyl, C 2-20 alkynyl, C 1-20 heteroalkyl, C 2-20 heteroalkenyl, C 2-20 heteroalkynyl, C 7-20 aralkyl, C 1-20 heteroalkylC 6-10 aryl, C 6-10 aryl, 5 or 6-membered heteroaryl or 5 or 6-membered heterocycle; wherein each of the foregoing groups may be optionally substituted with halogen, —CN, C 1-6 alkyl, C 6-10 aryl, —OR 2A where R 2A represents C 1-6 alkyl; and each of the alkyl, alkenyl and alkynyl moieties may be linear, branched or cyclic; wherein R EWG1 may further bear one or more acrylate groups and R EWG2 may further bear one or more methacrylate groups.
  • the methacrylate monomer (II) may be any suitable methacrylate monomer conventionally used in the art.
  • methacrylate monomer (II) may be a methacrylate monomer, a urethane methacrylate monomer, or an epoxy methacrylate monomer.
  • methacrylate resins are commercially available, for example from Sartomer, or Allnex (under the commercial name Ebecryl®):
  • methacrylate monomers we may mention:
  • urethane methacrylate monomers we may mention bifunctional urethane methacrylate monomers such as CN1963®.
  • epoxy methacrylate monomers we may mention bifunctional epoxy methacrylate monomers such as CN159®.
  • the nucleophilic monomer R 3A —NH—R 3B may be any compound bearing a primary or secondary amine functional group.
  • the nucleophilic monomer may not contain functional groups that may be more reactive towards the Michael acceptor double-bonds present on the electrophile monomer than primary or secondary amines, so as not to compete with the Aza-Michael reaction.
  • the nucleophilic monomer may contain —OH or —SH functional groups which are less reactive than primary or secondary amine functional groups towards Michael addition.
  • the nucleophilic monomer R 3A —NH—R 3B may be any of the primary amines described above for the first variant of the invention.
  • the nucleophilic monomer R 3A —NH—R 3B may be an aliphatic, cyclo-aliphatic or aromatic secondary amine. Examples include: N,N′-Dimethyl-1,6-hexanediamine, N,N′-Diethyl-2-butene-1,4-diamine, N,N′-Diisopropylethylenediamine, N,N′-Diisopropyl-1,3-propanediamine, N,N′-Dimethyl-1,3-propanediamine, N,N′-Diphenyl-p-phenylenediamine, 1,4,8,12-Tetraazacyclopentadecane.
  • the method according to the invention can generally be carried out using conventional methods of mixing the above described components in a suitable mixing device such as, but not limited to, stirred tanks, dissolvers, homogenizers, microfluidizers, extruders, or other equipment conventionally used in the field.
  • a suitable mixing device such as, but not limited to, stirred tanks, dissolvers, homogenizers, microfluidizers, extruders, or other equipment conventionally used in the field.
  • the process may further include a step of adding a material/reinforcement designed for this purpose using known methods.
  • the method further includes a step of impregnating composite reinforcements with the material obtained in step (i) in a mold, such as a silicone mold, prior to the application of light source.
  • a mold such as a silicone mold
  • the composite reinforcements may be any reinforcing conventionally used in the manufacture and implementation of composite materials.
  • the composite reinforcements may be selected from:
  • Vegetal fibers (hemp, flax . . . )
  • Mineral for example gravel, sand, glass beads, carbonate powder, alumina hydrate powder, steel powder, aluminum powder, polymer particles, titanium oxide, alumina, etc. . . . )
  • the composite reinforcements may be selected from glass fibers, carbon fibers, aramid fibers, basalt fibers, silica fibers, polymer fibers (such as polyesters, poly (p-phenylene-2,6-benzobisoxazole), aliphatic and aromatic polyamides, polyethylene, polymethyl methacrylate, polytetrafluoroethylene), natural fibers (such as nettle, flax or hemp fibers) . . .
  • the composite reinforcements may be previously disposed in a mold, and then impregnated by the composition obtained in step (i), before application of light radiation (step (ii)).
  • composite reinforcements may be pre-impregnated with the composition obtained in step (i). Then the mixture may be deposited/spread evenly over the mold, either manually or using an automated robot, in the case of mass production.
  • the process may further include a step of adding any other additive conventionally used in the field of resins, composite materials and applications.
  • suitable additives include:
  • tackifier refers to polymers which increase the tack properties, that is to say, the intrinsic viscosity or self-adhesion, the compositions so that, after a slight pressure a short period, they adhere firmly to surfaces.
  • the invention provides articles obtainable by a polymerization process according to any one variant of the inventive method, as described above.
  • the shape-memory polymer articles may be a composite, a wound-healing material/article, or an anti-scratch coating material.
  • the present invention offers many advantages, including:
  • Ethoxylated Bisphenol A Diacrylate (“EBAD”, also referred to as SR349®) was obtained from Sartomer, Irgacure 819® was procured from BASF. 1,5-diaminopentane (“DP”, cadaverine) was purchased from Sigma Aldrich.
  • the electrophile monomer e.g., EBAD
  • nucleophile monomer e.g., DP
  • Example 1 Three Stage Polymerization System (Cadaverine+EBAD)
  • Thermal properties of the different components were evaluated using Q200 from TA Instruments. Products were placed in hermetically sealed aluminium pans (between 5 and 10 mg) and heated from ⁇ 80 to 30° C. for stage 1 characterization, from ⁇ 40 to 40° C. for stage 2 characterization and from ⁇ 20 to 70° C. for stage 2 characterization (10° C. min ⁇ 1 ramp).
  • RT-FTIR Real Time Fourier Transform Infrared Spectroscopy
  • thermo-mechanical properties of the UV-cured materials were investigated with a Q800 DMA (TA Instruments) in the tensile configuration.
  • the samples were rectangular (12.8*5.3*0.070 mm) free films removed from polypropylene substrates. Temperatures ranged from ⁇ 20 to 100° C. (example 1) and ⁇ 20 to 140° C. (example 2) and the heating rate was set at 2° C./min. The amplitude and frequency of the oscillatory deformations were adjusted to 15 ⁇ m and 1 Hz, respectively
  • NMR calculated % transformation of the different species consumed or generated at different polymerization stage are displayed in FIG. 3 and Table 1.
  • Polymer glass transition temperature (Tg) and EBAD conversion are shown in Table 2.
  • Kinetic of EBAD-conversion during Stage 2 and Stage 3 is displayed in FIG. 4 .
  • Stage 1 polymer exhibits a low Tg of ⁇ 31° C. and a EBAD-conversion of 19%.
  • Photopolymerization of residual acrylates enabled stage 2 to increase Tg and EBAD-conversion. Indeed, a significant increase in both Tg (16° C.) and EBAD-conversion (79%) during stage 2 (photo-curing stage) was observed, in contrast to the first stage. Furthermore, it is possible to tune properties observed during second stage curing by changing the amount of remaining acrylate groups after stage 1.
  • stage 3 preserves the ability to polymerize in a vitrified media. Vitrification problem taking place in standard photopolymerization is not a limiting factor anymore. This crosslinking is, otherwise, controllable according to the initial ratio and the conversion obtained after stage 2.
  • the first stage takes advantage from the powerful click reaction called AZ1 that is orthogonal to the desired second stage reaction.
  • the AZ1 reaction forms a quasi-linear polymer the properties of which can be tuned by changing backbones, functionality of acrylate and/or amine. By bringing this reaction to an off-stoichiometric state, reactive acrylate moieties will be present in the media at the end of stage one.
  • Stage 2 is a photopolymerization step which is carried out in a particular window-time (between end of AZ1 and beginning of AZ2).
  • stage 3 the AZ2 reaction takes over and reaches a nearly total conversion. Indeed, by allowing sufficient time to finish the global aza-Michael reaction, it is possible to perform AZ2 in a rigid media.
  • This third reaction acts as another way to crosslink the material and helps to reach a higher conversion and a more homogeneous network. Indeed, FIG. 5 shows a decrease of the tan( ⁇ ) peak width during Stage 3.
  • Stage 1 Stage 2 Stage 3 (Stage 4) Conv Tg Conv Tg Conv Tg Conv Tg Conv Tg (%) (° C.) (%) (° C.) (%) (° C.) (%) (° C.) (%) (° C.) (%) (° C.) (%) (° C.) (%) (° C.) AZ 1 + AZ 2 25 ⁇ 31 50 ⁇ 11 AZ 1 + AZ 2 + 25 ⁇ 31 50 ⁇ 11 78 16 hv AZ 1 + hv(75) + 25 ⁇ 31 78 16 91 39 AZ 2 AZ 1 + hv(50) + 25 ⁇ 31 53 ⁇ 16 76 9 78 16 AZ 2 (+hv)
  • Example 2 Three Stage Polymerization System (Cadaverine+SR833s®)
  • Example 2 The same reaction protocol as Example 1 was used, replacing EBAD (SR349®) with SR833s (DP/SR833S ratio 1:4).
  • Three stage polymerization with feed molar ratio of 1:4 has been studied by NMR and DMA. Briefly, Irgacure 819® (2.5 wt %) was first added to the acrylate and then, the mixture was mixed with DP in a pillbox. After a determined reaction time, the mixture was both spread onto a polypropylene film (film thickness: 70 ⁇ m), samples were finally cured using a LED (395 nm) onto a conveyor belt with a dose of 7 J/cm2 (DMA data), Similar results to Example 1 were obtained. ( FIG. 6 , and Table 4).
  • Example 1 The same reaction protocol as Example 1 is used, replacing EBAD (SR349®) with HDDA. Similar results to Example 1 are obtained.
  • IPN network formation has been studied by RT-FTIR, DSC and DMA. Briefly, Irgacure 819® (2.5 wt %) was first added to the acrylate and/or methacrylate and then, the mixture (acrylate+methacrylate+irgacure819®) was mixed with DP in a pillbox while respecting amine:acrylate ratio of 1:1. After a determined reaction time, the mixture was both:
  • the method of the invention provides a new method for synthesizing IPN: a two step method combining a thermal polymerization step at room temperature (Aza-Michael click reaction) and a photopolymerization step.
  • Example 5A The same reaction protocol as Example 5A was used, replacing DP with N,N′-dimethyl-1,6-hexanediamine. Similar results to Example 5A were obtained.
  • Example 5A The same reaction protocol as Example 5A was used, replacing DP-EBAD with a mixture N,N′-dimethyl-1,6-hexanediamine-divinylsulfone in a ratio 1:1 Similar results to Example 5A were obtained.
  • Persoz hardness was determined using an Elcometer® Persoz Pendulum Hardness tester 220 V model (Persoz hardness of glass is 420 s). To characterize our samples, time taken for the amplitude of oscillation to decrease from 12° to 4° was characterized.
  • Flexibility/elongation is the pliability or rigidity of a material. It expresses the extent to which it resists bending. Pliability was investigated through a bend test. A mandrel with a diameter of 8 mm was used. Samples made on aluminium plates were hence bent uniformly on this mandrel and samples were examined (naked eyes) to point out the apparition of cracks or failures.
  • the film made according to the invention exhibits both a high hardness and an increased elasticity.
  • the film exhibited shape-memory properties, as evidenced in FIG. 9 .
  • Irgacure 819® (2.5 wt %) was first added to the acrylate and then, the mixture was mixed with DP in a pillbox. After a determined reaction time, the mixture was impregnated manually onto 6 plies of unidirectional glass fibers (450 g/m 2 ). The 6-ply samples were finally cured using a LED (395 nm) onto a conveyor belt with a dose of 14 J/cm 2 . Final samples had a thickness of 2 mm and were tested on an Instrom tensile test machine according to ISO 14130: Determination of apparent interlaminar shear strength by short-beam method.

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